Photopolymerizable compositions and process of making same

ABSTRACT

The embodiment of this disclosure provides for the method of preparing improved photopolymerizable noncrystalizing resinous film material and particularly of polyvalent metal salts of acrylic and methacrylic acids, and the products thereof.

United States Patent Inventor App]. No. Filed Patented AssigneePHOTOPOLYMERIZABLE COMPOSITIONS AND PROCESS OF MAKING SAME 9 Claims, NoDrawings U.S. C1 96/115, 204/15923 Int. Cl G03c 1/68 Field of Search...96/115; 204/159.24, 159.23; 260/526 U, 429, 431, 432, 435

References Cited UNITED STATES PATENTS 5/195 8 Fikentscher 260/526 U6/1961 Neugebauer 204/158 7/1963 Oster 96/30 3/1959 Oster 96/35 10/1967Baxendale et a1 204/15924 Primary Examiner-Norman G. Torchin AssistantExaminerEdward C. Kimlin Attorneys-James K. Haskell and Alton V.Oberholtzer ABSTRACT: The embodiment of this disclosure provides for themethod of preparing improved photopolymerizable noncrystalizing resinousfilm material and particularly of polyvalent metal salts ofacrylic andmethacrylic acids, and the products thereof.

PHOTOPOLYMERIZABLE COMPOSITIONS AND PROCESS OF MAKING SAME Thisinvention relates to improved photographic film material ofphotopolymerizable resinous film compositions and method of producingthe same. More particularly, the invention relates to the method ofpreparing improved compositions of photopolymerizable polyvalent metalsalts of acrylic and methacrylic acids, and products thereof.

The phenomenon of forming photographic images characterized by theformation of polymer particles due to photo induced polymerization ofpolymerizable compounds has been known in the art for many years.However, there has been the continuing problems of forming improved filmcompositions and enhancing photographic speed. Acrylic acid material hasappeared most suitable. However, may of the polyvalent metal salts ofacrylic and methacrylic acids have a limited solubility in water at roomtemperature and therefore are apt to crystallize before the desiredphotopolymerization can be effected. Consequently, in highconcentrations, difficulty is often encountered from precrystallizationbefore photopolymerization occurs. Thus, the preparation of desired andsuitable highcontent acrylate photographic films, in the wet or caststate, without normal or condensation crystallization therein has been aproblem. That is, with or without the removal of water, the highlyconcentrated metal acrylates have tendency to crystallize, or otherwisesometimes become unstable after preparation and standing before use.

It is accordingly an object of this invention or improvement to providethe art with new knowledge and teachings to overcome the above problemstherein.

Another object of this invention is to provide the art with thediscovery of my improvements in the method of preparing improved, morestable, light-sensitive photographically polymerizable resinousmaterial, and the products thereof, which uniformly serve as stablenoncrystallizing carriers of light-activable catalyst systems subject tophotopolymerizatron.

It is another object of this invention to provide the photographic artwith novel highly concentrated noncrystalline mixtures of polyvalentmetal salts of acrylic acid and methacrylic acid specifically suitablefor photopolymer photographic processes in the form of dry, glassy,amorphous, noncrystalline films, when mixed with or containing acatalyst system inactive in the absence of light and activated by light.

Another object of this invention is to provide the art with a method ofmaking stable, supersaturated, photosensitive noncrystallinecompositions of polyvalent metal acrylates having incorporated therewitha photosensitive polymerization catalyst system for polymer imagereproduction and the products thereof.

An additional object of this invention is to provide the art withimproved photosensitive polymerizable mixed metal acrylate compositionswhich, in highly concentrated forms, do not crystallize from solutionand have enhanced photographic speed in photopolymerization processeswhile providing greater photosensitivity and efficiency and possessing ahigher refractive index.

Further objects and advantages will become apparent from the followingnonlimiting details of disclosure illustrating and describing myinvention or improvements in providing the noncrystallizingphotosensitive film materials embodied herein. Such film materials areadapted to be utilized with reference to providing photographic filmshaving embodied therein a photosensitive catalyst as known to the artand more particularly and preferably the photoredox catalyst systems,with or without modification, and fixing a photopolymer image asdisclosed and embodied in my copending applications and the followingapplications. Such systems and modifications are provided in applicationSer. Nos. 483,986, (now abandoned and replaced by Ser. No. 824,902,450,397, (now abandoned and replaced by Ser. No. 824,903, 583,649,583,653, 583,696, 616,599 and Ser. No. 616,587 of John B. Rust,respectively. The compositions and processes therein are incorporatedherein by reference thereto for application and use with thephotosensitive film materials embodied in the present disclosure.

In addition, the noncrystalline compositions as provided herein arelikewise applicable to the products and processes as disclosed in theapplications of Leroy J. Miller and John B. Rust; Ser. Nos. 583,650 and583,652, and John D. Margerums Ser. No. 583,651, likewise includedherein by reference thereto. Thus, modifications utilizing the describedcomponents and systems described and embodied therein with the hereindescribed and embodied noncrystalline photopolymerizable polyvalentmetal salts of acrylic and methacrylic acids which do not crystallizefrom aqueous solutions even when highly concentrated, are embodiedherein.

In general, as indicated, the polyvalent metal salts of acrylic andmethacrylic acid and derived from metal oxides, metal hydroxides, metalcarbonates, and mixtures of the same, have only a limited solubility inwater, and when the solutions are concentrated beyond a certain point,crystallization occurs. As provided in the above applications, it isdisclosed therein that barium diacrylate possesses a fair solubility inwater, for example, at room temperature, thus providing solutionsthereof of higher solids content. While such solutions permitted thedevelopment of photographically more sensitive photosensitive films, themore highly concentrated solutions, for commercial production, are foundto be unstable. sometimes spontaneously crystallizing after preparationand compounding. With the improvement thereof as provided herein, moreconsistently stable compositions using barium diacrylate as the solepolyvalent metal component in highly concentrated metalacrylate-photoredox photosensitive compositons are now possible. Otherof the metal acrylates are of lesser or more limited solubility and themore particular embodiment herein is to provide noncrystallizing filmcompositions thereof in high and oversaturated concentrations, withoutany sign of crystallization or precipitation.

For example, lead diacrylate normally has only limited solubility inwater as has also cadmium diacrylate, neodymium triacrylate andstrontium diacrylate. l have found, however, that when added to bariumdiacrylate solution, the mixed polyvalent metal acrylate solution whichresults can be made in high concentration without any sign ofcrystallization or precipitation. Furthermore, the same and other mixedpolyvalent metal acrylate solutions, as described above, can be castinto films and dried to amorphous, noncrystalline, glasslike films.Also, when dried to a water-free condition in bulk, the mixed polyvalentmetal acrylate produces a glassy, amorphous noncrystalline solid.

I have also found that although lead diacrylate crystallizes out of a25% wt./vol. solution and mercuric diacrylate likewise crystallizes outof a 25% wt./vol. solution, that a solution containing about equal partsof lead diacrylate and mercuric diacrylate in a 25% wt./vol. solution isperfectly stable and does not crystallize when stored for an indefiniteperiod of time at room temperature. Somewhat different proportions allowsolutions of still higher concentrations to be prepared. This finding isparticularly important because it allows the preparation of concentratedphotosensitive film compositions comprising a photoredox catalyst andlead-mercuric diacrylate. The lead-mercuric diacrylate produces aninsoluble polymer having a refractive index greater than most polyvalentmetal acrylate polymers. The efficiency of a colloidal particle forscattering visible light is a function of the refractive index of theparticle relative to the medium in which it is embedded. Therefore, apolyvalent metal acrylate which yields a polymer whose refractive indexis higher than some other given polyvalent metal acrylate will givephotosensitive compositions of greater photographic speed, all otherfactors being equal. Lead and mercuric diacrylates give photopolymers ofquite high refractive index. Although lead diacrylate has only limitedsolubility in water, the mixed lead and mercuric diacrylates may be madeas substantially concentrated, noncrystallizing solutions which givecopolymers of relatively high refractive index and consequentlyphotosensitive compositions of greater photographic speed than, forinstance, the sole use of barium diacrylate in photosensitivecompositions. Such improved compositions thereof as provided herein,however, are also embodied herein.

EXAMPLE 1 To about 100 ml. of acrylic acid, there was addedapproximately 1 g. of activated carbon known to the trade as N UCHAR.The carbon was thoroughly suspended in the acrylic acid and allowed tostand at room temperature with stirring for several days. The acrylicacid was then filtered to remove the carbon.

157.5 g. of barium hydroxide octahydrate was ground to a fine powder ina mortar and partially dissolved and suspended in 135 ml. of distilledwater in a 500 ml. round bottom flask. Seventy two ml. of the filteredacrylic acid were added through a dropping funnel over a period of abouthour. After the addition of the acrylic acid, the nearly clear solutionwas allowed to stir for an additional 30 minutes. The slightly hazysolution was centrifuged yielding a clear, limpid solution of bariumdiacrylate having a concentration of 37.8 percent by weight.

EXAMPLE 2 About 100 ml. of acrylic acid were mixed with approximately lg. of activated carbon known to the trade as NUCHAR. The mixture wasstirred at room temperature for about 6 days, then the carbon removed bycentrifugation.

l 7.5 g. of barium hydroxide octahydrate was partially dis solved andsuspended in 157.5 ml. of distilled water and 72 ml. of centrifugedacrylic acid added dropwise over a period of 30 minutes. The hazysolution was stirred and heated at 6080 C. for 3 hours, then dividedinto two equal parts. One part was filtered hot through a bed offilteraid known to the trade as CELITE to yield a clear, limpidnoncrystallizing solution of barium diacrylate having a concentration ofabout 35.7 percent of weight. This solution is designated as solution A.The other part of the original solution was mixed with 4 g. of activatedcarbon known to the trade as NUCHAR and heated with stirring for anadditional 30 minutes at 60 -80 C. The treated solution was thenfiltered hot through a bed of filteraid known to the trade as CELlTEyielding a clear, limpid noncrystallizing solution of barium diacrylatehaving a concentration of about 35.7 percent by weight. This solution isdesignated as solution B.

EXAMPLE 3 157.5 g. of barium hydroxide octahydrate were ground to a finepowder in a mortar then suspended and partially dissolved in 157.5 ml.of distilled water in a 500 ml. round bottom flask. Seventy two ml. ofacrylic acid were added slowly over a period of 30 minutes to the bariumhydroxide and water with constant stirring. When all the acrylic acidhad been added, the solution was heated to 6580 C. with stirring for 2hours. Eight g. of activated carbon known to the trade as NUCHAR wasthen added and heating and stirring continued for an additional minutes.The hot solution containing the activated carbon was filtered through abed of filteraid known to the trade as CELlTE, yielding a clear, limpid,noncrystallizing solution of barium diacrylate having a concentration ofapproximately 35.7 percent by weight.

EXAMPLE 4 157.5 g. of barium hydroxide octahydrate were partiallydissolved and suspended in 157.5 ml. of distilled water IN a 500 ml.round bottom flask. Seventy-two ml. of freshly distilled acrylic acidwere added dropwise over a period of 30 minutes to the stirred bariumhydroxide and water. The hazy solution was then stirred and heated at60-80 C. for about 2 hours and, after this period, was divided into twoequal parts. One part was filtered hot through a bed of filteraid knownto the trade as CELlTE yielding a clear, limpid, noncrystallizingsolution of barium diacrylate having a concentration of about 35.7percent by weight. This solution was designated as solution A. To theother part of the original solution was added 4 g. of activated carbonknown to the trade as NUCHAR and the solution was stirred and heated at60-80 C. for an additional 30 minutes. This solution containing theactivated carbon was then filtered hot through a bed of filteraid knownto the trade as CELITE yielding a clear, limpid, noncrystallizingsolution of barium diacrylate having a concentration of about 35.7percent by weight. This solution was designated as solution B.

EXAMPLE 5 141.5 g. of barium hydroxide octahydrate were ground in amortar to a fine powder and mixed and 1 H g. of lead oxide (litharge,PbO). The mixture was partially dissolved and suspended in 157.5 ml. ofdistilled water and 72 ml. of acrylic acid were added dropwise withstirring over a period of 30 minutes. After all the acrylic acid hadbeen added, the solution was stirred and heated at 6080 C. for a periodof 2 178 hours. At this point, 8 g. of activated carbon known to thetrade as NUCHAR was added and stirring and heating continued for anadditional 20 minutes. The solution containing the activated carbon wasfiltered through a bed of filteraid known to the trade as CELITEyielding a clear. limpid, noncrystallizing solution of lead diacrylateand barium diacrylate having a concentration of approximately 37 percentby weight. Of the diacrylates present, the barium diacrylate isapproximately 90 mole percent and the lead diacrylate is about 10 molepercent. A portion of this solution was distilled under vacuum at about35 C. to remove water. The resulting concentrated solution wasnoncrystallizing clear, and had a viscosity that was somewhat higherthan the original solution. The barium diacrylate-lead diacrylatemixture had the same mole percent composition, but the final solutionhad a concentration of approximately 71.5 percent of solids by weight.

EXAMPLE 6 126.2 g. of powdered barium hydroxide octahydrate was mixedwith 22.3 g. oflead oxide (litharge, PbO). The mixture was partiallydissolved and suspended in 146.7 ml. of distilled water and 72 ml. ofdistilled acrylic acid added dropwise with stirring over a period of 30minutes. After all the acrylic acid had been added, the solution wasstirred and heated at 6080 C. for 2 hours. At this point, 8 g. ofactivated carbon known to the trade as NUCHAR was added and stirring andheating continued for an additional 20 minutes. The solution containingthe activated carbon was filtered hot through a bed of filteraid knownto the trade as CELlTE yielding a clear, limpid, noncrystallizingsolution of barium diacrylate and lead diacrylate having a concentrationof approximately 39.9 percent by weight. Of the diacrylates present, thebarium diacrylate is approximately mole percent and the lead diacrylateis about 20 mole percent.

When placed in a watch crystal and allowed to dry completely at roomtemperature by evaporation of the water, the composition remained clearthroughout the drying period and formed a clear, amorphous,noncrystalline film which was hard and glasslike. In a mixture, beforedrying, was incorporated a photosensitive polymerization catalyst system(as hereinafter examplifed and when exposed to a photographic negative,reproduced the negative in photopolymer image form.

EXAMPLE 7 94.7 g. of powdered barium hydroxide octahydrate was mixedwith 44.7 g. of lead oxide (litharge, PbO). The mixture was partiallydissolved and suspended in 153.7 ml. of distilled water and 72 ml. ofdistilled acrylic acid added dropwise with stirring over a period of 30minutes. After all the acrylic acid had been added, the solution wasstirred and heated at 60-80 C. for 2 hours. At this point, 8 g. ofactivated carbon known to the trade as NUCHAR was added and stirring andheating continued for an additional 20 minutes. The solution containingthe activated carbon was filtered through a bed of filteraid known tothe trade as CELITE. A clear, limpid solution was obtained while hot.The acrylate mixture contained 60 mole percent of barium diacrylate and40 mole percent of lead diacrylate. When cooled to room temperature, thesolution crystallized to a white pasty mass. From an inspection of theform of the crystals, it appeared that the lead diacrylate had been themajor component to crystallize out of solution.

EXAMPLE 8 Using the barium diacrylated-lead diacrylate solution of example 5 consisting of 90 mole percent of barium diacrylate and 10 molepercent of lead diacrylate and the barium diacrylate-lead diacrylatesolution of example 7 consisting of 60 mole percent of barium diacrylateand 40 mole percent of lead diacrylate, a series of solutions wereprepared by mixing the two above solutions to give a new solutioncontaining different mole percentages of barium and lead diacrylatesrespectively. Each of the new solutions was stored and inspected atintervals and dried films of each of the new solutions were prepared byevaporation at room temperature. Table I gives the results obtained fromthe series of new solutions. Generally, it appears that noncrystallizingsolutions can be prepared from the mixed diacrylates up to a mixturecontaining less than 40 mole percent of lead diacrylate. On the otherhand, clear, amorphous, hard, glasslike dry films can only result frommixtures containing from mole percent to 30 mole percent of leaddiacrylate and 80 mole percent to 70 mole percent of barium diacrylateinclusive. These limits might be extended slightly by using an expandedseries of the same and different metal acrylate mixtures.

35% concentration.

EXAMPLE 9 126.2 g. of powdered barium hydroxide octahydrate was ,mixedwith 12.9 g. of cadmium oxide powder. The mixture was partiallydissolved and suspended in 146.7 ml. of distilled water and 72 ml. ofacrylic acid added dropwise with stirring over a period of 30 minutes.After all the acrylic acid had been added, the solution was stirred andheated at 6080 C. for 2%hours. At this point, 8 g. of activated carbonknown to the trade as NUCHAR was added and stirring and heatingcontinued for an additional 30 minutes. The solution containing theactivated carbon was filtered hot though a bed of filteraid known to thetrade as CELITE yielding a clear, limpid, noncrystallizing solution ofbarium diacrylate and cadmium diacrylates having a concentration ofapproximately 38.4 percent by weight. Of the diacrylates present, thebarium diacrylate is approximately mole percent and the cadmiumdiacrylate is about 20 mole percent. The final solution had a pH ofabout 8.

When this solution was dried at room temperature, a clear, hard,transparent glasslike, noncrystalline film was formed.

In order to determine the photographic properties of the above solution,a photoredox catalyst prepared from:

2.14 g. sodium p-toluenesulfinate dihydrate 0.03 g. methylene blue ml.distilled water A photosensitive composition was prepared in the dark bymixing:

4 ml. Barium-cadmium diacrylate solution above 1 ml. Photoredox catalystsolution above. 7

This composition was placed between two glass plates separated by aperipheral shim spacer 7 ml. thick to form a uniform film 0.18 mm.thick. This film was exposed to a spot of light having an intensity atthe film surface of IO watts! cm The intensity of the light emergingfrom the back surface ofthefilm was monitored with a photomultipliertube and the electrical signal recorded on a strip chart recorder. Fromthis data, the optical density of the photosensitive composition at theilluminated spot was calculated as a function of exposure time. Theresults are given in table 2.

TABLE 2 Optical density Induction period 0.1 0.2 0.4 0.6 0.8 1.0

Time (seconds) 5.2 6.1 6.8 7.7 8.6 9.5 13.0

EXAMPLE 10 126.2 g. of powdered barium hydroxide octahydrate was mixedwith l6.8 g. of neodymium oxide. The mixture was partially dissolved andsuspended in 146.7 ml. of distilled water and 72 ml. of acrylic acidadded dropwise with stirring over a period of 30 minutes. After all theacrylic acid had been added, the solution was stirred and heated at60-80 C. for 2 U2 hours. At this point, 8 g. of activated carbon knownto the trade as NUCHAR was added and stirring and heating continued for30 minutes. The solution containing the activated carbon was filteredhot through a bed of filteraid known to the trade as CELITE yielding aclear, pale purple, limpid. noncrystallizing solution of bariumdiacrylate and neodymium triacrylate having a concentration ofapproximately 40.7 percent by weight. Of the acrylates present, thebarium diacrylate is approximately 80 mole percent and the neodymiumtriacrylate is about 20 mole percent. The solution had a pH of about 5.4When the solution was poured in a watch crystal and dried at roomtemperature, a clear, hard, transparent, noncrystalline, photosensitive,glasslike film was secured.

TABLE 3 Optical density Induction period 0.1 0.2 0.4 0.6 0.8 1.0

Time (seconds) 5.2 6.4 7.2 8.2 9.2 10.5 12.4

EXAMPLE 11 126.2 g. of powdered barium hydroxide octahydrate were mixedwith 14.8 g. of strontium carbonate. The mixture was partially dissolvedand suspended in 158 ml. of distilled water and 72 ml. of acrylic acidadded dropwise with stirring over a period of 30 minutes. After all theacrylic acid had been added, the solution was stirred and heated at69-80 C. for 4 1/2 hrs. At this point, 8 g. of activated carbon known tothe trade as NUCHAR was added and stirring the heating continued for anadditional 30 minutes. The solution containing the activated carbon wasfiltered hot through a bed of filteraid known to the trade as CELITEyielding a clear, limpid, noncrystallizing solution of barium diacrylateand strontium diacrylate having a concentration of approximately 36.8percent by weight. Of the diacrylates present, the barium diacrylate isapproximately 80 mole percent and the strontium diacrylate is about 20mole percent. The solution had a pH of about 5.6. When the solution waspoured into a watch crystal and dried at room temperature, a clear,hard, transparent, noncrystalline, photosensitive, glasslike film wassecured.

When the compositions as disclosed herein were mixed with aphotosensitive catalyst and dried, the films are photosensitive, as wellas having the additional advantageous characteristics as indicatedabove.

in order to determine the photographic characteristics of the abovesolution, a photosensitive composition was prepared in the dark bymixing:

4 ml. Barium strontium diacrylate solution above 1 ml. Photoredoxcatalyst solution described in example 9.

This composition was exposed to light under the conditions described inexample 9. The results of this example are given in table 4.

ln noncrystalline dried film form the photosensitive compositionreproduced a polymer image of an illuminated negative. As contemplatedand provided herein, the polymer image can be fixed.

EXAMPLE 12 21.8 g. of powdered mercuric oxide were mixed with 22.3 g. oflead oxide (litharge, PhD). The mixture was suspended in 200 ml. ofdistilled water. it was necessary to carry out the entire process ofthis example in the dark. Thirty mil. of distilled acrylic acid wereadded dropwise with stirring over a period of 30 minutes. After all theacrylic acid was added, the solution was stirred and heated at 40 C. for45 minutes. The solution was then filtered hot yielding a clear, limpid,noncrystallizing solution of mercuric diacrylate and lead diacrylatehaving a concentration of approximately 25 percent by weight. incontrast, lead diacrylate solutions of this concentration crystallizereadily at room temperature. Of the diacrylates present, the mercuricdiacrylate and the lead diacrylate are both approximately 50 molepercent. The solution had a pH of about 3.5.

In order to determined the photographic characteristics of the abovesolution, a photosensitive composition was prepared in the dark bymixing:

4 ml. Mercuric-lead diacrylate, solution above.

1 ml. Photoredox catalyst solution described in example 9 Thiscomposition was exposed to light under the conditions described inexample 9. In addition, for purposes of comparison, the solution ofbarium diacrylate of example 4, solution A, was diluted to give aconcentration of 25 percent by weight to be comparable to the solutionof this example. A photosensitive composition using this dilutedsolution of barium diacrylate was prepared in the same manner asdescribed above and exposed to light under the same conditions. Table 5gives the results of this example.

Comparable results were obtained with the solution above, containing thephotoredox catalyst system, when in noncrystalline dried film form. Uponexposure to an illuminated negative, the cast image therefrom wasreproduced in polymer form in the film.

In the above examples, the activated carbon is illustrated of anactivated absorbent. Other activated absorbents or sorbent material asthe art has known since 1932, described in a footnote 109 on page 315,in the publication, Technique of Or ganic Chemistry, Vol. 5, publishedby lnterscience Publishers 1951, and known as activated silica,activated alumina, activated zeolite, silic acid and the like, andmixtures thereof, may be used. In addition, as illustrated in example 8,by table 1, it is some times advantageous to independently prepareseparate metal acrylate solutions and then mix the separately preparedcompositions as binary, tertiary, quatinary, or higher, mixtures toprovide the clear, hard, transparent, noncrystalline, photosensitive,glasslike films.

Having described the present embodiments of my discovery in accordancewith the Patent Statutes, it will now be apparent that somemodifications and variations may be made without departing from thespirit and scope thereof. The specific embodiments described areprovided by way of illustration and are illustrative of my discovery,invention, or improvements which are to be limited only by the terms ofthe appended claims.

What is claimed is:

1. The method of preparing an improved photosensitive stable,supersaturated, polyvalent metal acrylate composition of enhancedphotopolymerizable photographic speed and useful in providing a stablenoncrystallizing photosensitive film thereof having 25 percent or morepolyvalent metal acrylate in photopolymerizable form comprising:

l. preparing a fresh clear batch of acrylic acid material selected fromthe group consisting of acrylic acid and methacrylic acid, and mixturesof said acids;

2. preparing a partially dissolved and suspended water mixture ofpowdered polyvalent metal material selected from the group consisting ofpolyvalent metal hydroxides, polyvalent metal oxides, polyvalent metalcarbonates, and mixtures of the same;

. mixing the said acrylic acid material of (l and the water mixture of(2);

4. stirring the mixture at from room temperature to about 85 C. for aperiod of from about 1 hour to several days;

5. adding activated sorbent material to the mixture and continuingstirring;

6. filtering and separating the said sorbent from the mixture,

and

7. recovering a clear, limpid, noncrystallizing solution of the metalacrylate present in an oversaturated concentration of at least 25percent noncrystallized nonprecipitated polyvalent metal acrylatecapable of producing a glassy amophous noncrystalline solid.

2. The method of claim 1 wherein the method of step 1 comprises:

i. suspending activated carbon in the said mixture of acrylic acidmaterial;

2. maintaining the suspension at room temperature with stirring;

3. separating the acrylic acid material from the activated carbon, and

4. recovering the said acrylic acid material as a clear batch.

3. The method of claim 1 wherein the powdered metal material is bariumhydroxide octahydrate.

4. The method of claim I wherein the powdered metal material is amixture of barium hydroxide octahydrate and lead oxide.

5. The method of claim 1 wherein the powdered metal material is amixture of barium hydroxide octahydrate and cadmium oxide.

6. The method of claim 1 wherein the powdered metal material is amixture of barium hydroxide octahydrate and neodymium oxide.

7. The method of claim 1 wherein the powder metal material is a mixtureof barium hydroxide octahydrate and strontium carbonate.

8. The method of claim 1 wherein the powdered metal material is amixture of mercuric oxide and lead oxide.

9. The method of claim 1 including the steps of heating the mixedsolution on the order of 6085 C. for a period of from about 2 hours toabout 4%hours and filtering the mixture.

2. preparing a partially dissolved and suspended water mixture ofpowdered polyvalent metal material selected from the group consisting ofpolyvalent metal hydroxides, polyvalent metal oxides, polyvalent metalcarbonates, and mixtures of the same;
 2. The method of claim 1 whereinthe method of step 1 comprises:
 2. maintaining the suspension at roomtemperature with stirring;
 3. separating the acrylic acid material fromthe activated carbon, and
 3. The method of claim 1 wherein the powderedmetal material is barium hydroxide octahydrate.
 3. mixing the saidacrylic acid material of (1 ) and the water mixture of (2);
 4. stirringthe mixture at from room temperature to about 85* C. for a period offrom about 1 hour to several days;
 4. The method of claim 1 wherein thepowdered metal material is a mixture of barium hydroxide octahydrate andlead oxide.
 4. recovering the said acrylic acid material as a clearbatch.
 5. The method of claim 1 wherein the powdered metal material is amixture of barium hydroxide octahydrate and cadmium oxide.
 5. addingactivated sorbent material to the mixture and continuing stirring; 6.filtering and separating the said sorbent from the mixture, and
 6. Themethod of claim 1 wherein the powdered metal material is a mixture ofbarium hydroxide octahydrate and neodymium oxide.
 7. The method of claim1 wherEin the powder metal material is a mixture of barium hydroxideoctahydrate and strontium carbonate.
 7. recovering a clear, limpid,noncrystallizing solution of the metal acrylate present in anoversaturated concentration of at least 25 percent noncrystallizednonprecipitated polyvalent metal acrylate capable of producing a glassyamophous noncrystalline solid.
 8. The method of claim 1 wherein thepowdered metal material is a mixture of mercuric oxide and lead oxide.9. The method of claim 1 including the steps of heating the mixedsolution on the order of 60* - 85* C. for a period of from about 2 hoursto about 4 1/2 hours and filtering the mixture.